CN110336002A - Nitrogen-doped carbon-coated zinc oxide composite nano material for lithium ion battery - Google Patents
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Abstract
The invention discloses a nitrogen-doped carbon-coated zinc oxide material used as a lithium ion battery and a preparation method thereof. The nitrogen-doped carbon-coated zinc oxide material is of a nano-particle structure, and nano-particles are loosely and disorderly arranged to form a porous microstructure. The nitrogen-doped carbon-coated zinc oxide is formed by hydrothermally synthesizing MOF precursor material and carbonizing the precursor MOF material at high temperature. The nitrogen-doped carbon-coated zinc oxide material is used as an electrode of the lithium ion battery100mA g ‑1 Shows 608 mAh g after 500 cycles of charge-discharge cycle at a current density of ‑1 The high specific capacity has stable cycle performance, and the preparation method has the advantages of simple operation, environmental protection and low cost, and is beneficial to industrialization.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to an oxide lithium ion battery electrode material and a preparation method thereof.
Background
With the social progress and the improvement of the living standard of people, electronic equipment such as mobile phones, cameras, notebook computers and the like are more and more popularized in the life of people, and the standby time and the service life of electronic products are closely related to those of energy storage devices of the electronic products. In this background, various energy storage devices, such as lead-acid batteries, zinc-manganese batteries, lithium ion batteries, and the like, have been developed. Among them, the lithium ion battery is a secondary battery that operates by insertion and extraction of lithium ions between electrodes, has been widely used in electronic devices, and has the following advantages: the voltage is high, and the working voltage of the lithium ion battery is higher than 3V; high specific capacity, the material can reach 150mAh g -1 The above specific capacities; the temperature range is wide, and the device can work in the environment of-25 to 45 ℃; the cycle life is long; high safety and no memory effect. Therefore, the lithium ion battery is receiving wide attention increasingly, and is widely applied in the field of consumer electronics, and has huge application space and potential in the fields of new energy automobiles, aerospace, military and the like.
The lithium ion battery mainly comprises a negative electrode, a diaphragm and an electrolyte, wherein a negative electrode material is one of core factors influencing the electrochemical performance of the lithium ion battery. How to obtain the cathode material with better performance is a difficult problem for researchers to overcome. To solve this problem, the main direction of research and development of supercapacitors should be to find new electrode materials with high specific capacity and long cycling stability. Designing the electrode material of the super capacitor comprises the following properties: (1) large specific capacity; (2) The oxidation-reduction potential is required to be lower, namely the working voltage is high; (3) The structure is not changed greatly in the process of lithium ion intercalation and deintercalation, namely, the lithium ion composite material has good cycle performance; (4) The lithium ion diffusion coefficient and the electronic conductivity are high, namely the internal resistance is low; and (5) the electrochemical stability is high, and the safety is good.
Lithium ion battery negative electrode materials can be largely classified into three types according to the manner of storing lithium. First, an intercalation material stores lithium by intercalating lithium ions into its layered structure, such as a carbon material, titanate, and the like, and has advantages of stable cycle performance but small specific capacity. Secondly, alloying negative electrode materials, such as Si, sn, sb and the like, form an alloy with lithium ions in the charging and discharging process to obtain higher specific capacity, but the volume expansion is serious in the charging and discharging process, and the cycle stability is poor. And thirdly, the conversion reaction cathode material, such as metal oxide, nitride, phosphide and the like, has a lower oxidation-reduction potential, so that the lithium ion battery can provide a higher working voltage, but the cycling stability is poorer. At present, the lithium ion battery has low specific capacity and poor cycling stability, which is a key and bottleneck link restricting the wide application of the lithium ion battery. Therefore, finding a composite electrode material with high specific capacity and long cycle life is the target of research and industrialization.
Transition metal oxides have been applied in the fields of catalytic degradation, energy storage, gas-sensitive sensing and the like, and at present, people have developed research on the application of metal oxides in lithium ion electrode materials. Zinc oxide is a cheap and environment-friendly transition metal oxide and has high specific capacity (the theoretical specific capacity is 987 mAh g) -1 ) But the conductivity is lower and the cycle stability is poorer along with larger volume change in the charging and discharging processes. The carbon material is a common lithium ion battery cathode material, has excellent cycling stability, but has low specific capacity (the specific capacity of a commercial graphite electrode is 372 mAh g) -1 ）。
Disclosure of Invention
The invention aims to solve the technical problems of lower specific capacity and poorer cycle stability of the lithium ion battery at present, designs a preparation method to prepare a novel composite material, can utilize the excellent cycle stability of a carbon material as a lithium ion battery cathode material and the advantage of high specific capacity of zinc oxide, and simultaneously overcomes the technical problems of low specific capacity of the carbon material and poorer cycle stability of the zinc oxide material caused by large volume change in the charge and discharge processes.
Based on the above purpose, the invention adopts the following technical scheme.
The invention provides a nitrogen-doped carbon-coated zinc oxide composite nano material for a lithium ion battery, which is a nano particle with a core-shell structure, wherein the diameter of the nano particle is 30-50 nm, the core is single hexagonal phase ZnO in a crystalline state, the shell is nitrogen-doped amorphous carbon, the thickness of nitrogen-doped amorphous carbon coated on the surface of the ZnO core is 2-5 nm, and the nano particles are loosely and disorderly arranged to form a porous structure.
The material is in a nano-particle form, the nano-scale particle size is favorable for improving the specific surface area, the contact area of the electrode material and the electrolyte is increased, the migration and the diffusion of lithium ions are favorable, more active points can be obtained, and the effect of improving the specific capacity of the electrode material is achieved; the carbon coating inhibits the volume change of the zinc oxide in the charging and discharging processes to a certain extent, improves the cycle stability, improves the conductivity of the electrode material, and accelerates the diffusion of lithium ions and electrons. The multi-electron nitrogen doping improves the conductivity of carbon, provides more lithium storage active sites and improves the specific capacity; the carbon-coated nitrogen doping can further improve the conductivity of carbon, and simultaneously, the carbon layer can obtain more lithium storage active points, so that the effect of enhancing the specific capacity of the electrode material is achieved, and high electrochemical performance is obtained.
The invention also provides a method for preparing the nitrogen-doped carbon-coated zinc oxide composite nano material, which comprises the following steps:
dissolving raw materials of zinc nitrate hexahydrate and glycollic acid in absolute ethyl alcohol, ultrasonically stirring uniformly at room temperature, and placing in a reaction kettle for hydrothermal synthesis reaction; after the reaction is finished, naturally cooling the reaction kettle to room temperature, collecting a solid product, washing and drying to obtain a Zn-containing MOF (metal organic framework) precursor; and carbonizing the precursor under the Ar gas protective atmosphere, and then cooling to room temperature along with the furnace to obtain the nitrogen-doped carbon-coated zinc oxide composite nano material.
Further, the molar ratio of zinc nitrate hexahydrate to glycolic acid is 1, the ratio parameter needs to be accurately controlled, and if the error of the ratio exceeds 1% in the experiment of the inventor, the nitrogen-doped carbon-coated zinc oxide composite nano material cannot be obtained.
Further, absolute ethanol was added in a volume of 4 mL per 1 mmol of glycolic acid.
Further, the temperature of the hydrothermal synthesis reaction of the reaction kettle in an oven is 160 ℃, and the reaction time is 10 to 24h.
Further, the carbonization temperature is 400 to 600 ℃, and the heating rate is 2 ℃ for min -1 The carbonization heat preservation time is 4 hours, the carbonization parameter is established by the inventor through a plurality of experiments, and the nitrogen-doped carbon-coated zinc oxide composite nano material can not be prepared when the carbonization parameter exceeds the range established by the growth parameter.
The invention also provides application of the nitrogen-doped carbon-coated zinc oxide composite nano material which is taken as a lithium ion battery cathode material and has the volume of 100mA g -1 The current density of the capacitor is 500 cycles of charge and discharge, and the capacitor still has 608 mAh g -1 The specific capacity of the material shows high specific capacity and excellent cycling stability.
The preparation method of the invention utilizes metal organic framework to obtain the nitrogen-doped carbon-coated zinc oxide composite nano material to be designed through simple carbonization treatment, forms nitrogen-doped carbon layer coating on the surfaces of zinc oxide nano particles, improves the diffusion rate of lithium ions and electrons, inhibits the volume change of the zinc oxide material in the charging and discharging process to a certain extent, has high specific capacity and good cycling stability, not only utilizes the advantages of excellent cycling stability of the carbon material as the lithium ion battery cathode material and high specific capacity of zinc oxide, but also overcomes the technical problems of low specific capacity of the carbon material and poor cycling stability of the zinc oxide material due to the electric conductivity and large volume change in the charging and discharging process, thereby obtaining the excellent lithium ion battery cathode material.
The beneficial results of the invention are as follows:
(1) The nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared by the method disclosed by the invention has the high specific capacity characteristic of a transition metal oxide, is favorable for improving the specific capacity of a battery, and also has the long cycle stability of a carbon material, and is favorable for prolonging the service life of the battery.
(2) According to the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared by the method, the surface of the nano zinc oxide is coated with the nitrogen-doped amorphous carbon with the thickness of 2-5 nm, and the carbon layer is favorable for diffusion of lithium ions and electrons, so that the conductivity of the material is improved; meanwhile, the carbon layer can inhibit the volume change of the zinc oxide in the charging and discharging induction process to a certain extent, and the cycling stability of the battery is improved. The nitrogen doping can further improve the conductivity of the carbon, and simultaneously, the carbon layer can obtain more lithium storage active points, so that the effect of enhancing the specific capacity of the electrode material is achieved, and high electrochemical performance is obtained.
(3) The nitrogen-doped carbon-coated zinc oxide composite nanomaterial for the supercapacitor prepared by the method disclosed by the invention has high specific capacity and excellent cycle stability, is an excellent lithium ion battery cathode material, and can be applied to long-life lithium ion battery products.
(4) The invention adopts the method of hydrothermal synthesis and high-temperature carbonization, has simple operation, short flow and low cost, and is beneficial to industrialized production.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 3 is an XRD pattern of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 4 is a cyclic voltammogram of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 5 is a constant current charging and discharging plateau curve diagram of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 6 is a graph of the cyclic constant current charge and discharge specific capacity of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1.
Fig. 7 is an ac impedance spectrum of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial fabricated in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Dissolving raw materials of 10 mmol of zinc nitrate hexahydrate and 10 mmol of glycollic acid in 40 mL of absolute ethanol, performing ultrasonic treatment at room temperature, uniformly stirring, placing the mixture into a reaction kettle, placing the reaction kettle into a drying oven to perform hydrothermal synthesis reaction at 160 ℃ for 16 hours, cooling to room temperature, washing and drying to obtain a Zn-containing MOF precursor; and (3) putting the obtained MOF precursor into a tube furnace, carbonizing at 500 ℃ in an argon atmosphere, heating at a rate of 2 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain a final product, namely the nitrogen-doped carbon-coated zinc oxide composite nanomaterial.
Example 2
Dissolving raw materials of 10 mmol of zinc nitrate hexahydrate and 10 mmol of glycollic acid in 40 mL of absolute ethanol, performing ultrasonic treatment at room temperature, uniformly stirring, placing the mixture into a reaction kettle, placing the reaction kettle into a drying oven to perform hydrothermal synthesis reaction at 160 ℃ for 12 hours, cooling to room temperature, washing and drying to obtain a Zn-containing MOF precursor; and (3) placing the obtained MOF precursor in a tube furnace, carbonizing at 400 ℃ under the argon atmosphere, heating up at the rate of 2 ℃/min, keeping the carbonization temperature for 4 hours, and cooling to room temperature to obtain a final product, namely the nitrogen-doped carbon-coated zinc oxide composite nano material.
Example 3
Dissolving 10 mmol of zinc nitrate hexahydrate and 10 mmol of glycolic acid in 40 mL of absolute ethanol, performing ultrasonic treatment at room temperature, uniformly stirring, placing in a reaction kettle, placing the reaction kettle in a drying oven for hydrothermal synthesis reaction at 160 ℃ for 10 hours, cooling to room temperature, washing and drying to obtain a Zn-containing MOF precursor; and (3) putting the obtained MOF precursor into a tube furnace, carbonizing at 600 ℃ under the argon atmosphere, heating at a rate of 2 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain a final product, namely the nitrogen-doped carbon-coated zinc oxide composite nanomaterial.
Example 4
Dissolving raw materials of 10 mmol of zinc nitrate hexahydrate and 10 mmol of glycollic acid in 40 mL of absolute ethanol, performing ultrasonic treatment at room temperature, uniformly stirring, placing the mixture into a reaction kettle, placing the reaction kettle into a drying oven to perform hydrothermal synthesis reaction at 160 ℃ for 20 hours, cooling to room temperature, washing and drying to obtain a Zn-containing MOF precursor; and (3) putting the obtained MOF precursor into a tube furnace, carbonizing at 450 ℃ in an argon atmosphere at the heating rate of 2 ℃/min for 4 hours, and cooling to room temperature to obtain the final product, namely the nitrogen-doped carbon-coated zinc oxide composite nanomaterial.
Example 5
Dissolving 10 mmol of zinc nitrate hexahydrate and 10 mmol of glycolic acid in 40 mL of absolute ethanol, performing ultrasonic treatment at room temperature, uniformly stirring, placing in a reaction kettle, placing the reaction kettle in a drying oven for hydrothermal synthesis reaction at 160 ℃ for 24 hours, cooling to room temperature, washing and drying to obtain a Zn-containing MOF precursor; and (3) putting the obtained MOF precursor into a tube furnace, carbonizing at 550 ℃ under the argon atmosphere, heating at a rate of 2 ℃/min, keeping the temperature for 4 hours, and cooling to room temperature to obtain a final product, namely the nitrogen-doped carbon-coated zinc oxide composite nanomaterial.
And (3) performance testing:
1) And (4) SEM test: the nitrogen-doped carbon-coated zinc oxide nanoparticle material prepared in each of the above embodiments was observed under a scanning electron microscope to show that the material was in an irregular nanoparticle shape. For example, fig. 1 shows the micro-morphology of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1, and it can be seen that the nitrogen-doped carbon-coated zinc oxide composite nanomaterial is irregular nanoparticles, the diameter of the nanoparticles is 30 to 50 nm, and the nanoparticles are loosely and disorderly arranged to form a porous structure. The nanoscale particle size is beneficial to improving the specific surface area, increasing the contact area of the electrode material and the electrolyte, and being beneficial to the migration and diffusion of lithium ions, and simultaneously more active points can be obtained, thereby achieving the effect of improving the specific capacity of the electrode material.
2) TEM test: the nitrogen-doped carbon-coated zinc oxide nanoparticle material finally obtained in each example is observed under a transmission electron microscope, and the surface of the zinc oxide nanoparticle is coated with a layer of nitrogen-doped amorphous carbon with the thickness of 2-5 nm. For example, fig. 2 is a TEM image of the nitrogen-doped carbon-coated zinc oxide composite nanomaterial prepared in example 1, which shows that the nitrogen-doped carbon-coated zinc oxide composite nanomaterial is a nanoparticle having a core-shell structure, the diameter of the nanoparticle is 30 to 50 nm, the core is crystalline ZnO, the shell is nitrogen-doped amorphous carbon, and the thickness of the amorphous carbon coated on the surface of the ZnO core is 2 to 5nm. The energy spectrum test of the TEM sample shows that: the amorphous carbon layer contains significant nitrogen because the carbon layer used as the shell layer is a nitrogen-doped amorphous carbon material. The carbon coating inhibits the volume change of the zinc oxide in the charging and discharging process to a certain extent, improves the cycle stability, improves the conductivity of the electrode material, and accelerates the diffusion of lithium ions and electrons. The doping of multi-electron nitrogen improves the conductivity of carbon, provides more lithium storage active sites and improves the specific capacity.
3) XRD test: XRD tests are carried out on the finally obtained samples prepared in the above examples, and the finally prepared materials are confirmed to be ZnO single phase. For example, FIG. 3 is an X-ray diffraction pattern of the sample obtained in example 1, wherein the diffraction peaks of the sample are seen to correspond to the characteristic peaks of ZnO, and the product obtained has a single hexagonal phase of ZnO in the core layer. No XRD peak of carbon was observed, indicating that it is amorphous carbon.
4) And (3) electrochemical performance testing: the materials prepared in the above examples are respectively assembled into a 2032 type button cell to be tested for electrochemical performance, and FIG. 4 shows that the assembled cell of the sample prepared in example 1 is at 0.5mV s -1 The CV curve under the sweep rate can be seen to have obvious oxidation reduction peaks; FIG. 5 is a graph of the charge and discharge curves of the assembled battery of samples made in example 1 at different current densities with a distinct plateau; FIG. 6 is a graph of the current density of 100mA g of the assembled battery of the sample prepared in example 1 -1 The discharge specific capacity chart of the charge-discharge cycle under the condition still has 608 mAh g after 500 times of charge-discharge cycles -1 The capacity of (2) indicates that the material has good cycling stability and high specific capacity; fig. 7 is an ac impedance plot of the sample prepared in example 1, which shows that the internal resistance of the material is only 4.4 ohms, indicating that the material is very conductive.
Claims (5)
1. A nitrogen-doped carbon-coated zinc oxide composite nano material for a lithium ion battery is characterized in that: the nitrogen-doped carbon-coated zinc oxide composite nano material is nano particles with a core-shell structure, the diameter of the nano particles is 30-50 nm, the core of the nano particles is single hexagonal phase ZnO in a crystalline state, the shell of the nano particles is nitrogen-doped amorphous carbon, the thickness of the nitrogen-doped amorphous carbon coated on the surface of the ZnO core is 2-5 nm, and the nano particles are loosely and disorderly arranged to form a porous structure.
2. The nitrogen-doped carbon-coated zinc oxide composite nanomaterial for the lithium ion battery according to claim 1, wherein: the internal resistance of the nitrogen-doped carbon-coated zinc oxide composite nano material lithium ion battery negative electrode material is 4.4 ohms; at 100mA g -1 At a current density of 608 mAh g, charge and discharge cycles of 500 cycles -1 The specific capacity of (A).
3. A method of making the nitrogen-doped carbon-coated zinc oxide composite nanomaterial of claim 1 or 2, comprising the steps of:
dissolving raw materials of zinc nitrate hexahydrate and glycollic acid in absolute ethyl alcohol, ultrasonically stirring uniformly at room temperature, and placing in a reaction kettle for hydrothermal synthesis reaction; after the reaction is finished, naturally cooling the reaction kettle to room temperature, collecting a solid product, washing and drying to obtain a Zn-containing MOF precursor; carbonizing the precursor under the protection of Ar gas, and then cooling to room temperature along with the furnace to obtain the nitrogen-doped carbon-coated zinc oxide composite nanomaterial;
wherein the molar ratio of zinc nitrate hexahydrate to glycolic acid is 1;
anhydrous ethanol was added as required to volume 4 mL per 1 mmol of glycolic acid.
4. The method for preparing the nitrogen-doped carbon-coated zinc oxide composite nanomaterial according to claim 3, wherein the method comprises the following steps: the temperature of the hydrothermal synthesis reaction of the reaction kettle in an oven is 160 ℃, and the reaction time is 10 to 24h.
5. The method for preparing the nitrogen-doped carbon-coated zinc oxide composite nanomaterial according to claim 3, wherein the method comprises the following steps: the carbonization temperature is 400 to 600 ℃, and the heating rate is 2 ℃ for min -1 The carbonization heat preservation time is 4 hours.
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| CN113161533A (en) * | 2021-04-08 | 2021-07-23 | 中北大学 | MOF-derived ZnO @ C composite material and application thereof |
| CN113782731A (en) * | 2021-08-20 | 2021-12-10 | 中南大学 | Cathode material for water-based zinc secondary battery and preparation method thereof |
| CN113782731B (en) * | 2021-08-20 | 2022-11-22 | 中南大学 | Cathode material for water-based zinc secondary battery and preparation method thereof |
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